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At least 721 records · Page 40

The Kinetics of the Coherent Stage of Hydroxide Corrosion on Li 2 O-Covered LiH

The capability to model LiOH growth on vacuum-baked LiH is a necessary precursor to making kinetic predictions of undesirable hydrogen outgassing from corroded LiH materials when placed in sealed-system applications. Here, in this work, LiH samples with initial LiOH surface corrosion layers less than 1.1 μm were outgassed by vacuum baking at high temperature to convert LiOH to Li 2 O. Diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy was used to measure the subsequent LiOH regrowth during exposure to 25–375 ppm of H 2 O vapor at room temperature. Logarithmic kinetics best model the growth of this coherent hydroxide corrosion layer (up to 1.5 μm) on previously vacuum-baked LiH samples. The logarithmic kinetics are attributed to the dissociation of H 2 O on the corrosion layer and the establishment of a H + /OH – electric field across the thickening LiOH corrosion layer. A time-dependent model of LiOH corrosion growth as a function of both initial LiOH thickness before vacuum baking and moisture partial pressures during re-exposure was developed to help researchers better assess the unwanted hydrogen outgassing potential from LiH/LiD materials.

Matt, Sarah M. [Lawrence Livermore National Labora↗

Effect of decades of corrosion on the microstructure of altered glasses and their radiation stability

Understanding the microstructural evolution of glasses during their interaction with water and radiation is of fundamental importance in addressing the corrosion of nuclear waste forms under geological disposal conditions. Here we report the results of more than 21 years of corrosion of two borosilicate glasses showing the formation of mesoporous C–S–H gels in Ca-bearing glasses and a mainly microporous microstructure in Al-bearing glasses. These porous corroded glasses were then irradiated with heavy ions to simulate the effects of recoil nucleus damage and monitored in real time using transmission electron microscopy with in situ ion irradiation. The ballistic collisions remarkably healed the porous corroded glasses to a pore-free homogeneous microstructure. Besides providing new insights and predictions about how doped glasses and actual waste forms may evolve under corrosion and irradiation, the results highlight the non-universal nature of the existing corrosion models and the important role that the glass composition and radiation damage play in the evolution of the microstructure during corrosion.

36 MATERIALS SCIENCE↗

Intergranular corrosion of Ni-30Cr in high-temperature hydrogenated water after removing surface passivating film

Abstract High-resolution transmission electron microscopy and atom probe tomography are used to characterize the initial passivation and subsequent intergranular corrosion of degraded grain boundaries in a model Ni-30Cr alloy exposed to 360 °C hydrogenated water. Upon initial exposure for 1000 h, the alloy surface directly above the grain boundary forms a thin passivating film of Cr 2 O 3 , protecting the underlying grain boundary from intergranular corrosion. However, the metal grain boundary experiences severe Cr depletion and grain boundary migration during this initial exposure. To understand how Cr depletion affects further corrosion, the local protective film was sputtered away using a glancing angle focused ion beam. Upon further exposure, the surface fails to repassivate, and intergranular corrosion is observed through the Cr-depleted region. Through this combination of high-resolution microscopy and localized passive film removal, we show that, although high-Cr alloys are resistant to intergranular attack and stress corrosion cracking, degradation-induced changes in the underlying metal at grain boundaries make the material more susceptible once the initial passive film is breached.

(S)TEM↗

Electron beam surface remelting enhanced corrosion resistance of additively manufactured Ti-6Al-4V as a potential in-situ re-finishing technique

This study explores the effect of surface re-finishing on the corrosion behavior of electron beam manufactured (EBM) Ti-G5 (Ti-6Al-4V), including the novel application of an electron beam surface remelting (EBSR) technique. Specifically, the relationship between material surface roughness and corrosion resistance was examined. Surface roughness was tested in the as-printed (AP), mechanically polished (MP), and EBSR states and compared to wrought (WR) counterparts. Electrochemical measurements were performed in chloride-containing media. It was observed that surface roughness, rather than differences in the underlying microstructure, played a more significant role in the general corrosion resistance in the environment explored here. While both MP and EBSR methods reduced surface roughness and enhanced corrosion resistance, mechanical polishing has many known limitations. The EBSR process explored herein demonstrated positive preliminary results. The surface roughness (R a ) of the EBM-AP material was considerably reduced by 82%. Additionally, the measured corrosion current density in 0.6 M NaCl for the EBSR sample is 0.05 µA cm –2 , five times less than the value obtained for the EBM-AP specimen (0.26 µA cm –2 ).

42 ENGINEERING↗

Glass-contact refractory of the nuclear waste vitrification melters in the United States: a review of corrosion data and melter life

The performance of the refractory lining in glass melters used for nuclear waste vitrification is critical to the melter reliability for long-term continuous operation. Monofrax® K-3, a high Cr 2 O 3 fused cast refractory material, has been widely used to build the liners of nuclear waste glass melters in the United States. Corrosion behaviour of Monofrax® K-3 refractory has been evaluated based on crucible-scale testing, inspection of the refractory components following scaled melter testing, and inspections of the Defense Waste Processing Facility (DWPF) melter refractory after service. The literature generally consists of empirical models based on short-term testing to describe refractory corrosion dependence on glass composition. Corrosion data from tests with longer testing times, at various temperatures, in the presence of molten salts, and with different redox reactions in the plenum atmosphere exist, may be insufficient to provide accurate refractory service life estimates. Additionally, the corrosion data collected under actual and scaled melter operating conditions are limited. Recommendations to achieve more direct correlation between the laboratory refractory corrosion data predictions and the observed melter service life are discussed to allow for more accurate predictions of the useful life of melter refractory linings.

Jin, Tongan↗

Mechanical and Corrosion Assessment of Friction Self-Piercing Rivet Joint of Carbon Fiber-Reinforced Polymer and Magnesium Alloy AZ31B

In the present work, thermoset carbon fiber–reinforced polymer (CFRP) was spot joined to magnesium alloy AZ31B by a friction self-piercing riveting (F-SPR) process. Lap shear tensile and cross-tension testing were used to evaluate the mechanical joint performance. An average lap shear tensile load of 5.18 kN was achieved, while an average of 2.81 kN was found from cross-tension testing. All F-SPR samples showed a pullout of AZ31B after mechanical testing, indicating good mechanical interlocking between the steel rivet and AZ31B. Corrosion potential was measured for each material to establish the galvanic corrosion characteristics. As expected, AZ31B was found to be the most active, while thermoset CFRP was the most noble. The steel rivet fell between the AZ31B (active) and the thermoset CFRP (noble). Salt fog corrosion testing (ASTM B-117) was performed to evaluate the corrosion performance of the uncoated F-SPR joint. With up to 200 h of exposure, the post-corroded F-SPR joint integrity retained 81.2% of the pre-exposure F-SPR joint strength with AZ31B pullout failure mode. From cross-sectional analysis of the F-SPR joint, extensive corrosion of AZ31B was observed at the joint and other exposure areas. However, steel rivet was not significantly corroded due to sacrificial anode effect by which AZ31B corroded first in the galvanic couple.

36 MATERIALS SCIENCE↗

MECHANICAL AND CORROSION ASSESSMENT OF FRICTION SELF-PIERCING RIVET JOINT OF CARBON FIBER-REINFORCED POLYMER AND MAGNESIUM ALLOY AZ31B

In the present work, thermoset carbon fiber–reinforced polymer (CFRP) was spot joined to magnesium alloy AZ31B by a friction self-piercing riveting (F-SPR) process. Lap shear tensile and cross-tension testing were used to evaluate the mechanical joint performance. An average lap shear tensile load of 5.18 kN was achieved, while an average of 2.81 kN was found from cross-tension testing. All F-SPR samples showed pull-out of AZ31B after mechanical testing, indicating good mechanical interlocking between the steel rivet and AZ31B. Corrosion potential was measured for each material to establish the galvanic corrosion characteristics. As expected, AZ31B was found to be the most active, while thermoset CFRP was the most noble. The steel rivet fell between the AZ31B (active) and the thermoset CFRP (noble). Salt fog corrosion testing (ASTM B-117) was performed to evaluate the corrosion performance of the uncoated F-SPR joint. With up to 200 h of exposure, the post-corroded F-SPR joint integrity retained 81.2% of the pre-exposure F-SPR joint strength with AZ31B pull-out failure mode. From cross-sectional analysis of the F-SPR joint, extensive corrosion of AZ31B was observed at the joint and other exposure areas. However, steel rivet was not significantly corroded potentially due to sacrificial anode effect by which AZ31B corroded first in the galvanic couple.

Lim, Yong Chae↗

Potential–Dependent BDAC Adsorption on Zinc Enabling Selective Suppression of Zinc Corrosion for Energy Storage Applications

Utility-scale zinc (Zn) batteries are a promising solution to address the problem of intermittency of renewable energy sources; however, Zn-metal anodes in these batteries suffer from capacity loss due to spontaneous corrosion of the Zn especially when high-surface area anode configurations are employed. Additionally, Zn dendrites are known to form during battery charging limiting the cycle-life of these batteries. Electrolyte additives have been explored that prevent aforementioned issues, but these too come at a cost, i.e., surface-blocking additives polarize the electrode surface leading to loss in the voltaic and energy efficiencies of the battery. In this contribution, a novel electrolyte additive, benzyldimethylhexadecylammonium chloride (BDAC), is investigated for its ability to suppresses corrosion of Zn in an acidic (pH = 3) electrolyte. An attribute of BDAC distinct from previously studied additives is that it selectively suppresses electrochemical activity when the Zn electrode is at its corrosion potential; however, during high-rate Zn deposition (charging) or stripping (discharging), BDAC is essentially deactivated and thus it does not appreciably polarize the electrode surface, thus minimizing voltaic efficiency losses. This selective corrosion suppression behavior is explored using slow-scan voltammetry, which reveals hysteresis implying a potential- or current-dependent BDAC adsorption mechanism in which BDAC reaches higher surface coverages when the partial currents at the Zn surface are low (e.g., at or near the corrosion potential), but BDAC coverage is reduced considerably when the Zn deposition or stripping rates are increased. Numerical simulations of the BDAC diffusion-adsorption process corroborate this mechanism. Ramifications of our approach to the selective suppression of Zn dendrites are discussed.

25 ENERGY STORAGE↗

Atomistic Modeling of Corrosion Events at the Interface between a Metal and Its Environment

Atomistic simulation is a powerful tool for probing the structure and properties of materials and the nature of chemical reactions. Corrosion is a complex process that involves chemical reactions occurring at the interface between a material and its environment and is, therefore, highly suited to study by atomistic modeling techniques. In this paper, the complex nature of corrosion processes and mechanisms is briefly reviewed. Various atomistic methods for exploring corrosion mechanisms are then described, and recent applications in the literature surveyed. Several instances of the application of atomistic modeling to corrosion science are then reviewed in detail, including studies of the metal-water interface, the reaction of water on electrified metallic interfaces, the dissolution of metal atoms from metallic surfaces, and the role of competitive adsorption in controlling the chemical nature and structure of a metallic surface. Some perspectives are then given concerning the future of atomistic modeling in the field of corrosion science.

Taylor, Christopher D.↗

Stainless and carbon steel corrosion in aqueous piperazine at absorber and water wash conditions

Corrosion of carbon steel (C1010) and stainless steels (304, 316L, 430) was measured at absorber and water wash conditions at the bench scale. Corrosion rate decreases with increasing concentration of piperazine (PZ). With more than 0.003 m PZ in solution, carbon steel has acceptable corrosion performance. Corrosion of carbon steel increases with increasing partial pressure of CO2, suggesting loading is another dominant parameter. The effect is more significant for dilute PZ; therefore, untreated flue gas with high CO2 content should be avoided in the water wash. Temperature has a less significant effect than PZ concentration and loading. Carbon steel corrosion increases with increasing flow velocity at both absorber and water wash conditions

Liu, Ching-Ting↗

Materials corrosion of high temperature alloys immersed in 600°C binary nitrate salt

Thirteen high temperature alloys were immersion tested in a 60/40 binary nitrate salt. Samples were interval tested up to 3000 hours at 600ÀC with air as the ullage gas. Chemical analysis of the molten salt indicated lower nitrite concentrations present in the salt, as predicted by the equilibrium equation. Corrosion rates were generally low for all alloys. Corrosion products were identified using x-ray diffraction and electron microprobe analysis. Fe-Cr based alloys tended to form mixtures of sodium and iron oxides, while Fe-Ni/Cr alloys had similar corrosion products plus oxides of nickel and chromium. Nickel based alloys primarily formed NiO, with chromium oxides near the oxide/base alloy interface. In625 exhibited similar corrosion performance in relation to previous tests, lending confidence in comparisons between past and present experiments. HA230 exhibited internal oxidation that consisted of a nickel/chromium oxide. Alloys with significant aluminum alloying tended to exhibit superior performance, due formation of a thin alumina layer. Soluble corrosion products of chromium, molybdenum, and tungsten were also formed and are thought to be a significant factor in alloy performance.

Kruizenga, Alan Michael↗

Corrosion of high temperature alloys in solar salt at 400, 500, and 680ÀC.

Corrosion tests at 400, 500, and 680ÀC were performed using four high temperature alloys; 347SS, 321SS In625, and HA230. Molten salt chemistry was monitored over time through analysis of nitrite, carbonate, and dissolved metals. Metallography was performed on alloys at 500 and 680ÀC, due to the relatively thin oxide scale observed at 400ÀC. At 500ÀC, corrosion of iron based alloys took the form of chromium depletion and iron oxides, while nickel based alloys also had chromium depletion and formation of NiO. Chromium was detected in relatively low concentrations at this temperature. At 680ÀC, significant surface corrosion occurred with metal losses greater than 450microns/year after 1025hours of exposure. Iron based alloys formed complex iron, sodium, and chromium oxides. Some data suggests grain boundary chromium depletion of 321SS. Nickel alloys formed NiO and metallic nickel corrosion morphologies, with HA230 displaying significant internal oxidation in the form of chromia. Nickel alloys both exhibited worse corrosion than iron based alloys likely due to preferential dissolution of chromium, molybdenum, and tungsten.

Kruizenga, Alan Michael↗

Micro-Continuum Modeling of Nuclear Waste Glass Corrosion

The purpose of this contribution is to report on preliminary nano-continuum scale modeling of nuclear waste glass corrosion. The focus of the modeling is an experiment involving a French glass SON68 specimen leached for 25 years in a granitic environment (Guittonneau et al., 2011; Gin et al., 2011; Gin et al., 2013). The 25 year experiment carried out by French scientists offers a unique opportunity to examine the controls on the rate of nuclear glass corrosion under controlled experimental conditions using a borosilicate glass of the kind widely considered for nuclear waste storage. The long term experiment makes it possible to move beyond the initial rate stage, with direct measurements of the longer term, residual rates of corrosion. Important in this regard is whether the rate of corrosion shows a parabolic dependence on time, as would be expected from a conventional diffusion model in which the reaction products (amorphous silica-rich gel) create a diffusion barrier that grows in width over time, or whether the time dependence is linear (Guittonneau et al., 2011). A linear dependence on time would call into question the model of a Passive Reactive Interface (PRI) presented by Cailleteau et al. (2008), although it does not entirely preclude such a model if the interface maintains a constant width over time (forming at the leading edge next to the pristine glass and dissolving at the trailing edge). The leachate concentration measurements collected every 56 days over 25 years by Guittonneau et al. (2011) provide data to constrain the long term corrosion rate and its time dependence.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Inorganic Corrosion-Inhibitive Pigments for High-Temperature Alkali-activated Well Casing Foam Cement

This study evaluates inorganic pigments for improving carbon steel (CS) brine-corrosion protection by the sodium metasilicate-activated calcium aluminate cement/Fly Ash blend at 300 °C. Calcium borosilicate (CBS) and zinc phosphate, significantly improved CS corrosion-protection by decreasing cement’s permeability for corrosive ions and inhibiting anodic corrosion. An amorphous Na 2 O-Al 2 O 3 -SiO 2 -H 2 O phase tightly attached to CS surface formed at 300 °C in CBS-modified cement pore solution. The corrosion rate of the CS covered with this phase was nearly 4-fold lower than in the case of nonmodified cement pore solution where the major phase formed on the surface of CS was crystalline analcime.

15 GEOTHERMAL ENERGY↗

Inorganic Corrosion-Inhibitive Pigments for High-Temperature Alkali-activated Well Casing Foam Cement

This study evaluates inorganic pigments for improving carbon steel (CS) brine-corrosion protection by the sodium metasilicate-activated calcium aluminate cement/Fly Ash blend at 300°C. Calcium borosilicate (CBS) and zinc phosphate, significantly improved CS corrosion-protection by decreasing cement’s permeability for corrosive ions and inhibiting anodic corrosion. An amorphous Na 2 O-Al 2 O 3 -SiO 2 -H 2 O phase tightly attached to CS surface formed at 300oC in CBS-modified cement pore solution. The corrosion rate of the CS covered with this phase was nearly 4-fold lower than in the case of nonmodified cement pore solution where the major phase formed on the surface of CS was crystalline analcime.

15 GEOTHERMAL ENERGY↗

FY17 Status Report: Research on Stress Corrosion Cracking of SNF Interim Storage Canisters.

This progress report describes work done in FY17 at Sandia National Laboratories (SNL) to assess the localized corrosion performance of container/cask materials used in the interim storage of spent nuclear fuel (SNF). Of particular concern is stress corrosion cracking (SCC), by which a through-wall crack could potentially form in a canister outer wall over time intervals that are shorter than possible dry storage times. Work in FY17 refined our understanding of the chemical and physical environment on canister surfaces, and evaluated the relationship between chemical and physical environment and the form and extent of corrosion that occurs. The SNL corrosion work focused predominantly on pitting corrosion, a necessary precursor for SCC, and process of pit-to-crack transition; it has been carried out in collaboration with university partners. SNL is collaborating with several university partners to investigate SCC crack growth experimentally, providing guidance for design and interpretation of experiments.

36 MATERIALS SCIENCE↗

Collective Summary of sCO2 Materials Development Part II: High-Temperature Alloy Corrosion Behavior within Compact Heat Exchangers.

Materials compatibility is a major concern for the design and operation of supercritical carbon dioxide (sCO2) power cycles. Two areas were recently identified for which very little prior knowledge was available. These were the behavior of polymer materials in low-temperature sCO2 environments as well as the high-temperature corrosion behavior for alloys that have been fabricated into compact heat exchangers. A critical need exists to increase understanding in both areas. As such, the Sandia sCO2 Materials Development program initiated a series of experiments for both areas in FY19. The progress that has been made in understanding the behavior of polymers in sCO2 was summarized in the Part I report, while this Part II report describes progress in the area of compact heat exchanger corrosion. For the compact heat exchangers being developed for use in supercritical CO2 power cycles, alloy corrosion is important to understand as it may lead to reduced flow path area, reduced heat transfer, and blocked flow channels. The fabrication of these heat exchangers involve thermal processes such as brazing or diffusion bonding, where the influence of these processes on the corrosion behavior of the alloys is unknown. Candidate alloys for these heat exchangers are typically evaluated for corrosion behavior as witness coupons, without being subjected to these thermal processes. To close this gap in understanding, a series of experiments were completed that utilized small heat exchanger samples subjected to flowing CO2 for 500 hours at 750°C. Small sections of the heat exchanger samples were characterized before and after the 500 hour exposure in order to characterize the oxide growth in the channels as well as the hardness of the alloys. Results are compared to witness coupons of the same alloys.

36 MATERIALS SCIENCE↗

Analysis of Microbial Communities as Indicators of Microbially Induced Corrosion Potential in Stainless Steel Piping

The 200 West Area Pump-and-Treat (200W P&T) facility is part of the final remedy decision for the 200 ZP-1 Operable Unit (OU) and is the interim remedial action for 200-UP-1 OU at the Hanford Site. The facility also treats water from other sources across the site, including 200-DV-1 OU perched water, groundwater from the 200-BP-5 OU, and leachate from the Environmental Restoration Disposal Facility. The facility originally operated a biological treatment process for nitrate that resulted in systemic biofouling and loss of injection well capacity, requiring frequent and costly well rehabilitation. Biofouling has also contributed to corrosion of welds and pitting of stainless-steel piping at the facility. The biological treatment for nitrate was suspended at the end of 2019 calendar year to eliminate negative impacts from biological treatments which improve facility operations and treatment of carbon tetrachloride. Evaluation of the 200W P&T facility’s response to operational improvements, specifically the suspension of the biological treatment, provides information on the potential for continued microbially induced corrosion (MIC). To this end, historical data sets (2015-2017) were compared with molecular biological analyses of 200W P&T water samples from 2018-2020 to quantify trends in total microbial biomass and specific microbial indicator species (iron, sulfate, nitrate, and manganese reducing bacteria) known to cause and enhance metal corrosion. Results showed unequivocal reductions (in excess of 90%) in all microbiological indicators measured following the suspension of the biological treatment. Although abundance measurements for all corrosive MIC populations initially declined after removal of the treatment system, nitrate-reducing bacteria (nirK) and sulfate-reducing bacteria remain highly abundant in the system, an order of magnitude higher than the number of cells present prior to the removal of the biological treatment system [5.14e (1.4) cells/L, vs. 1.14e (0.07) cells/L, reported as average (±SD) for n=3]. In addition, there was an unexpected inflection point in 2019 where all microbial indicators increased unexpectedly in abundance in 2020 by as much as two orders of magnitude compared to 2019 samples. Given the limited number of water samples available for this analysis, the cause of the increase in microbial indicators post-biological treatment has not yet been determined. Systematic sampling of the facility for continued monitoring is recommended so that the responses of MIC populations can be evaluated to ensure that further corrosion is avoided, allowing the 200W P&T facility to operate safely and efficiently at design capacity.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗